Glass fiber reinforced elastomers

ABSTRACT

This invention is addressed to the improvement in the bonding relationship between glass fibers and elastomeric materials, wherein glass fibers are treated with a composition formulated to contain a resorcinol-aldehyde resin, a butadiene-styrene vinyl pyridine terpolymer, an incompatible wax and a dicarboxylated butadiene-styrene resin.

1, :1 tpg 1 Jan. 22, 197% GLASS lFllBER REINFORCED ELASTOMERS William111. Utfner, Newark, Ohio Assignee: Owens-Coming Fiberglas Corporation,Toledo, Ohio Filed: Apr. 24,1972

Appl. No.: 230,723

Inventor:

us. (:1. ..117/72. 57/140 G, 57/153. 117/126 GB, 260/285 B. 260/8461111.01 1332b 17/10, B32b 25/02 Field of Search... 57/153, 140; 260/285B, 846; 117/126 GB, 72

References Cited UNITED STATES PATENTS 3/1971 .lanetos et a] 117/126 GBPrimary ExaminerWi11iam D. Martin Assistant Examiner-William H. SchmidtAttorney, Agent, or Firm-Carl G Staelin et a1.

[57] ABSTRACT This invention is addressed to the improvement in thebonding relationship between glass fibers and elastomeric materials,wherein glass fibers are treated with a composition formulated tocontain a resorcinolaldehyde resin, a butadiene-styrene vinyl pyridineterpolymer, an incompatible wax and a dicarboxylated butadiene-styreneresin.

17 Claims, 3 Drawing Figures GLASS FIBER REINFORCED ELASTOMERS Thisinvention relates to glass fiber-elastomeric products, and moreparticularly to the treatment of glass fibers and compositions in thetreatment of glass to facilitate the combination of glass fibers withelastomeric materials such as the manufacture of glass fiberreinforcedelastomeric products.

The term glass fibers, as used herein, is intended to refer to andinclude (l) continuous fibers formed by the rapid attenuation ofhundreds of streams of molten glass and to strands formed when suchcontinuous glass fiber filaments are gathered together in forming; andto yarns and cords formed by plying and/or twisting a number of strandstogether, and to woven and nonwoven fabrics which are formed of suchglass fiber strands, yarns or cords, and (2) discontinuous fibers formedby high pressure steam or air or other attenuating force directedangularly downwardly onto multiple streams of molten glass issuing froma glass melting bushing and to yarns that are formed when suchdiscontinuous fibers are allowed to rain down gravitationally onto aforaminous surface wherein the fibers are gathered together to form asliver which is drafted into a yarn; and to woven and non-woven fabricsformed of such yarns of discontinuous fibers, and (3) combinations ofsuch continuous and discontinuous fibers in strands, yarns, cords andfabrics formed thereof.

As used herein, the term elastomer is intended to mean and includenatural rubber in the cured or uncured stage, vulcanized or unvulcanizedstage, and synthetic organic elastomeric materials such as nitriles,acrylics and esters and particularly copolymers of butadiene with theseand terpolymers thereof with styrene and synthetic rubbers asrepresented by butadiene polymers and copolymers with monoolefins suchas butadiene-styrene copolymer, butadiene-acrylonitrile copolymers,butadiene-styrene vinyl pyridine terpolymers, chloroprene, isoprene,neoprene, isobutyl rubber and the like elastomeric polymers andcopolymers in their cured or uncured stages, and vulcanized orunvulcanized stages. Included also are the EPDM rubbers, such as formedby the interpolymerization of ethylene, an alpha-monoolefin having fromthree to twenty carbon atoms, such as propylene, and a polyene, such asdicylopentadiene, 1,4-hexadiene and preferably an alkylene or alkylidenenorbornene, such as S-alkylidene- 2-norbornene and the like in which thealkylidene group numbers from two to twelve carbon atoms, andpolysulfone rubbers.

It is now well known to combine glass fibers with elastomeric materialsin the manufacture of glass fiberreinforced elastomeric products, suchas driving belts, timing belts, pneumatic tires, etc. One of theproblems which has been encountered in such combinations of glass fiberswith elastomeric products is the problem of securely anchoring the glassfiber surfaces to the elastomeric material in which the glass fibers aredistributed. It is believed that this problem stems in part from thefact that the glass fibers are completely smooth, rodlike members and'inpart from the fact that the glass fiber surfaces are highly hydrophilicin nature thereby resulting in the formation of a thin but tenaciousfilm of moisture on the glass fiber surfaces which serves to destroy anybond, chemical or physical, which would otherwise be formed between theglass fiber surfaces and the elastomeric material with which the glassfibers are combined.

To minimize the problems of binding the glass fiber surfaces to theelastomeric materials, it has been the practice in the manufacture ofglass fiber-reinforced elastomeric products to make use of glass fibersin the form of individual glass fibers having a coating on the surfacesthereof to intertie the individual glass fibers to the elastomericmaterial in which the glass fibers are distributed, or preferably glassfibers in the form of yarns, cords or fabrics, hereinafter referred toas bundles, containing an impregnant therein which also serves tointertie the glass fiber bundles to the elastomeric material in whichthe bundles are distributed.

One such composition which can be used in the treatment of individualglass fibers or bundles of glass fibers as outlined above is describedin US. Pat. No. 3,567,671 in which description is made of a treatingcomposition formulated to include a resorcinolaldehyde resin, abutadiene-styrene-vinyl pyridine terpolymer, a latex component and anincompatible wax. As the latex component, use can be made of copolymersof vinyl chloride and vinylidene chloride, an acrylic resin latex in theform of a polymethylmethylacrylate latex or a carboxylatedbutadiene-styrene resin latex.

The carboxylated butadiene styrene resin latex suggested for use in thecomposition of the foregoing patent is a monocarboxylated systemprepared by copolymerization of butadiene and styrene in aqueousemulsion in the presence of a small amount of an ethylenicallyunsaturated carboxylic acid, and is commercially available from theChemical Division, Goodyear Tire and Rubber Company in Akron, Ohio,under the trade name Pliglite 4 8( While compositions of the typedisclosed and claimed in the foregoing patent represent a significantadvance in the art in the treatment of glass fibers for use asreinforcement for elastomeric materials, there is nevertheless room forimprovement in the stability of such systems and in the adhesion betweenthe treated glass fibers and elastomeric materials with which the glassfibers are combined.

It is accordingly an object of the present invention to provide animproved composition for use in the treatment of individual glass fibersto form a thin coating on the surfaces thereof, or preferably for use inthe treatment of bundles of glass fibers, as by impregnation, to promotethe bonding relationship of glass fibers with elastomeric materials inthe manufacture of glass fiberreinforced elastomeric products.

It is a more specific object of the invention to provide an improvedcomposition for the treatment of glass fibers having improved stability,low viscosity growth in use and minimum scumming characteristics.

It is a related object of the invention to produce coated glass fibersand impregnated bundles of glass fibers for use as reinforcement forelastomeric materials which are characterized by improved adhesioncharacteristics.

These and other objects and advantages of the invention will appear morefully hereinafter, and, for purposes of illustration, but not oflimitation, embodiments of the invention are shown in the accompanyingdrawing in which:

FIG. 1 is a schematic illustration of one method for the impregnation ofa bundle of glass fibers in accordance with the preferred practice ofthe invention;

FIG. 2 is a cross-sectional view of a bundle of glass fibers treated inaccordance with the method illustrated in FIG. 1; and

FIG. 3 is a cross-sectional view of glass fibers individually coatedwith the composition of this invention in accordance with anotherembodiment thereof.

The concepts of this invention reside in an improved composition for usein the treatment of glass fibers formulated to include, as the essentialcomponents, a resorcinol-aldehyde resin, a vinylpyridine-butadienestyrene terpolymer, an incompatible wax and adicarboxylated butadiene-styrene resin. It has been unexpectedly foundthat the use of a dicarboxylated butadiene-styrene resin in the glassfiber treating composition is capable of providing treated glass fibershaving significantly greater adhesion to elastomeric materials when thetreated glass fibers are combined with elastomeric materials in themanufacture of glass fiberreinforced elastomeric products as compared tocompositions of the type described in the foregoing patent containing amonocarboxylated butadiene-styrene resin. In addition, thedicarboxylated butadiene-styrene resin provides a glass fiber treatingcomposition having greater stability, which is less susceptible to scumformation during use and which exhibits very low viscosity growth onaging.

As used herein, the term dicarboxylated butadienestyrene resin refers tobutadiene-styrene copolymers prepared by copolymerization of butadieneand styrene in the presence of a small amount of a dicarboxylic acidcontaining ethylenic unsaturation. The ratio of styrene to butadiene isat least 50/50, and is preferably within the range of 50/50 to 85/15.Such resins are commercially available in the form of latices from theChemical Division of the Goodyear Tire and Rubber Co. in Akron, Ohio,under the trade names Pliolite 4000, Pliolite 4264, Pliolite 4121,Pliolite 4303, Pliolite 386, Pliolite 402 and Pliolite 388.

Without limiting the present invention as to theory, it is believed thatthe clean running characteristics as well as the improved stability ofthe composition of this invention can be attributed at least in part tothe fact that the dicarboxylated resin latices used in the practice ofthis invention contain small amounts of emulsifiers, frequently lessthan 2 percent by weight and of the order of about 1 percent by weight.Monocarboxylated butadiene-styrene resin latices generally contain 4percent to 6 percent by weight emulsifier which, it is believed,frequently contributes to scum formation.

Another distinction of the dicarboxylated butadienestyrene resin systemsused in the practice of this invention, as compared to themonocarboxylated system of the prior art, resides in the fact that thedicarboxylated systems are self-reactive. Whereas the monocarboxylatedresin requires the use of a curing agent such as zinc oxide ormelamine-formaldehyde condensates, the dicarboxylated butadiene-styreneresins are capable of cure or cross-linking by heat alone with the useof extraneous curing agents. Again, without limiting the presentinvention as to theory, it is believed that the ability of thedicarboxylated butadiene-styrene resins to undergo heat initiatedcross-linking materially contributes to the improved adhesioncharacteristics of the treated glass fibers.

The dicarboxylated butadiene-styrene resin preferably constitutes from15 to 40 parts by weight, and preferably 20 to 30 parts by weight, on adry solid basis, of the composition of the invention.

The resorcinol-aldehyde resin component of the composition of thisinvention contributes materially to the adhesion of the resultingcomposition to the perfectly smooth, non-porous hydrophilic glass fibersurfaces, and is preferably a resin formed by reaction of the resorcinolwith a lower aliphatic aldehyde containing one to three carbon atoms,such as formaldehyde, acetaldehyde and propionaldehyde. Preferred resinsfor use in the present invention are resorcinolforrnaldehyde resinswhich are formed by the condensation reaction of formaldehyde withresorcinol in a mole ratio of about 2 moles of resorcinol to 1 mole offormaldehyde. Suitable resins are commercially available such as, forexample, Penacolite R2170 from the Koppers Company in the form of asolution containing percent solids. In general, use is preferably madeof an amount of resorcinol-aldehyde resin to provideresorcinol-formaldehyde resin solids within the range of 2 to 10 partsby weight, and preferably within the range of 3 to 8 parts by weight.

As the butadiene-styrene vinyl pyridine terpolymer, use can be made of anumber of such terpolymers which are well known to those skilled in theart. Such terpolymers frequently contain about 70 percent by weightbutadiene, 15 percent by weight styrene and about 15 percent by weightvinyl pyridine, although these proportions can be varied and are notcritical to the practice of this invention. Representative of suitablebutadiene-styrene vinyl pyridine terpolymers include the terpolymersavailable from the Goodyear Tire and Rubber Company under the trade namePliolite VP" and a number of terpolymers available from the General Tireand Chemical Company under the trade name Gentac. For example, use ispreferably made of Gentac FS which is a terpolymer having acomparatively low Mooney viscosity within the range of 35-45, althoughuse can also be made of Gentac 107" which is a terpolymer having ahigher Mooney viscosity, generally within the range of 1 10-120. It hasbeen found that generally superior results have been obtained with theuse of Gentac FS since the lower Mooney viscosity of the materialcontributes improved adhesion characteristics of the resulting treatedglass fibers.

One vinyl pyridine-butadiene-styrene terpolymer which is particularlywell suited for use in the composition of this invention is a terpolymermarketed by the Goodyear Tire and Rubber Company under the productdesignation LPF4545A. This particular latex system contains about thesame relative amounts of vinyl pyridine, butadiene and styrene, butcontains less emulsifier, usually less than 2 percent by weight. It isbelieved that the low emulsifier content of this terpolymer contributesto the stability of the overall treating composition.

The terpolymer component is generally employed in an amount sufficientto provide from 20-60 parts by weight, and preferably 35-50 parts byweight, of the terpolymer in the treating composition on a dry solidsbasis.-

The butadiene-styrene-vinyl pyridine terpolymer, the

dicarboxylated butadiene-styrene resin, and the resorcinol-formaldehyderesin are all compatible, each with the other, and operate to coat thefibers and fill the interstices between the fibers when applied as animpregnant in a glass fiber bundle whereby the fibers making up thebundle are capable of realignment in the direction of stress formaximizing the high strength properties of the impregnated bundle. Thecomponents are also somewhat compatible with the elastomeric materialsforming the continuous phase of a glass fiberelastomeric product tothereby permit glass fibers treated in accordance with the presentinvention to be blended with such elastomeric materials for advancementto a cured ur vulcanized stage whereby the treating material from theglass fiber bundles becomes an integral part of the elastomeric phase tointertie the treated glass fibers to the elastomeric material.

The incompatible wax component of the present invention is preferably amicro-crystalline paraffinic wax of the type described in theforementioned patent, and without limiting the present invention as totheory, it is believed that the wax serves at least a limited functionas a rubber softener. The wax is normally employed in an amount inexcess of that capable of remaining compatible with the solids makeup ofthe remainder of the treating composition whereby the wax componentsweats out for concentration on the surfaces of the treated glass fibersor glass fiber bundles to provide a non-tacky surface and thereby permittreated glass fibers to be processed into yarns, threads, cords orfabrics, and/or to be wound onto and unwound from spools without seizureof binding, notwithstanding the elastomeric component with which thefibers are treated. Thus, the glass fibers can be treated with acomposition that enhances good adhesion to the surfaces of glass fiberswithout interfering with the subsequent processing characteristics ofthe glass fibers. The composition also contains the necessary componentsto facilitate the bonding relationship between the glass .fiber surfacesand the elastomeric material in the manufacture of glassfiber-reinforced elastomeric products. 4

The wax preferred for use in the present 57571665 is a micro-crystallineparaffinic wax having a melting point within the range of 145-150 F andsold under the designation Vultex Wax Emulsion No. 9" by the GeneralLatex and Chemical Corp. As will be appreciated by those skilled in theart, other paraffinic microcrystalline waxes having the describedcharacteristics can be employed in the practice of this invention inlieu of or in addition to the Vultex wax specifically described. Theamount of the wax component can be varied within the range of 3-25 partsby weight, and preferably 4-20 parts by weight, of the dry solids of thetreating composition.

Having described the basic concepts of this invention, reference is nowmade to the following examples, which are provided by way ofillustration and not by way of limitation, of the practice of thisinvention in treating glass fibers for subsequent combination withelastomeric materials in the manufacture of glass fiberreinforcedelastomeric products. In the preferred practice of the invention, aglass fiber bundle, in the form of one or more strands of fibers or inthe form of a cord I composed of two or more strands of glass fibersplied and/or twisted together, is subjected to impregnation with thecomposition of the invention. The glass fibers forming the bundlepreferably have a thin size coating on the individual surfaces of thefibers from a conventional size composition such as one of those sizecompositions described in U.S. Pat. No. 3,424,608.

An impregnating composition representative of the concepts of theinvention is prepared from the following EXAMPLE 1 PART A:

732 parts by wt. deionized water 1 part by wt. sodium hydroxide 48 partsby wt. resorcinol-formaldehyde polymer in the form of a latex containingsolids (Penacolite R2170) 16 parts by wt. formalin (37% formaldehyde)PART B:

900 parts by wt. butadiene-styrene-vinyl pyridine terpolymer (42%solids) (Gentac PS) parts by wt. ammonium hydroxide PART C:

200 parts by wt. water 15 parts by wt. ammonium hydroxide 350 parts bywt. dicarboxylated butadiene -styrene resin (50% solids) (Pliolite 4121)parts by wt. micro-crystalline paraffin wax (melting point 150F.)-Vultex Wax Emulsion No. 9 of General Latex and Chemical Corp. 56%solids) Part A of the foregoing example is separately prepared bycombining the ingredients, and the resulting mixture is aged for a fewminutes with the alkali present to adjust the pH to 6 to 7. Theremainder of the ingredients are then combined and the various parts aremixed together. However, it will be appreciated that variations in theorder of mixing can be carried out to provide a stable system, dependingsomewhat upon the nature of the components and the relative amountsemployed. it has been found that aging of the entire mixture is notessential, although best results are generally obtained when theresulting composition is aged for 0 10-24 hours or even longer prior touse in impregnating glass fiber bundles.

impregnation with the aqueous composition prepared in accordance withExample 1 can be carried out by way of any of a variety of knowntechniques for the impregnation of glass fiber bundles. Referringspecifically to FIG. 1 of the drawing, a strand 10 formed of a pluralityof glass fibers which have preferably, although not necessarily, beensized in forming, is passed over a guide roller 12 for passagedownwardly into an impregnating bath 14 containing the aqueousimpregnating composition of Example 1. The bundle is then passed under apair of rollers 16 to effect a sharp bend in the bundle which operatesto open the bundle to facilitate more complete penetration of theaqueous treating composition in the bundle of glass fibers for completeimpregnation of the bundle. The impregnated bundle is then raised fromthe bath for passage through a roller or die 18 which operates to removeexcess treating composition from the bundle and to work the treatingcomposition into the bundle. Thereafter, the endless bundle is advancedover roller 20 into a drying oven 22, such as a dielectric, microwave,hot gas, or radiant oven maintained at a temperature above ambienttemperature, and preferably a temperature within the range of 6S180 F.,to accelerate removal of the aqueous diluent and to set the impregnantin situ in the glass fiber bundle. Drying will occur within a relativelyshort period of time, generally within 0.1 sec. to 3 min., dependingupon the temperature of drying.

The resulting bundle is shown in cross section in FIG. 2 of the drawing.As can be seen from this figure, the bundle is formed of a plurality ofglass fibers 40 which have an optional size coating 42 on the surfacesof the individual filaments. The impregnant 44 in the form of the solidsfrom the treating composition of this invention completely penetratesthe bundle and serves to separate the glass fibers each from the otherto form a unitary bundle structure.

Additional examples of this concept of the present invention may beillustrated by the following:

EXAMPLE 2 EXAMPLE 3 PART A:

730 parts by wt. distilled water 1.5 parts by wt. tetramethyl ammoniumhydroxide 48 parts by wt. resorcinol-formaldehyde latex (75% solids) 16parts by wt. formalin I PART B:

900 parts by wt. butadiene-styrene-vinyl pyridine terpolymer (Gentacl0742% solids) 80 parts by wt. ammonium hydroxide 100 parts by wt. water350 parts by wt. dicarboxylated butadiene-styrene resin (50% solids) 100parts by wt. Vultex Wax Emulsion No. 9(56% solids) EXAMPLE 4 PART A:

732 parts by wt. distilled water 1.5 parts by wt. ammonium hydroxide 48parts by wt. resorcinol-formaldehyde (75% solids) 16 parts by wt.formalin PART B:

900 parts by wt. butadiene-styrene-vinyl pyridine terpolymer (42%solids) (LPF 4545A) 80 parts by wt. ammonium hydroxide 350 parts by wt.dicarboxylated butadiene-styrene resin (50% solids) (Pliolite 4121) 50parts by wt. Vultex Wax Emulsion No. 9(56% solids) Part A in each of theabove examples is separately prepared by combining the ingredients. Theremainder of the ingredients are combined and the various parts are thenmixed together. Aging of the entire mixture is not essential butbeneficial results accrue, such as greater adhesion and stabilization ofthe mixture, after aging the entire mixture for from 10-24 hours beforeuse to impregnate the glass fiber bundle.

The foregoing compositions are prepared in accordance with the proceduredescribed in Example 1, and the resulting compositions can be applied byimpregnation to glass fiber bundles in accordance with the proceduredescribed in Example 1. In general, the impregnating compositions usedin the practice of this invention are diluted with sufficient water toprovide a composition having a solids content within the range of 10-50percent by weight. Application of the impregnating composition can bemade in an amount sufficient to impregnate with dry solids of 5-30percent by weight of the glass fiber bundle, and preferably 10-25percent by weight. It is desirable to achieve as full impregnation aspossible into the bundles of glass fibers to more effectively separatethe fibers each from the other with the impregnating material since thesolids are effective to cushion the fibers and to protect the fibersfrom destruction by mutual abrasion. The deeper the penetration, themore effective is the bond between the bundles of glass fibers and theelastomeric material with which the bundles of glass fibers are combinedin the subsequent manufacture of glass fiber-elastomeric products.

The elastomeric material with which the impregnated bundle of glassfibers is combined constitutes a continuous phase. The elastomerconstituting the continuous phase may be selected from elastomers of thetype incorporated into the impregnating composition, or the elastomericmaterial may differ therefrom. The elastomer constituting a continuousphase can be employed in the cured or uncured stage or in the vulcanizedor unvulcanized stage. It is believed that the tie-in between theimpregnated bundle of glass fibers and the elastomer constituting thecontinuous phase occurs primarily during cure or vulcanization of theelastomeric materials in combination with the impregnated bundles.

More complete protection for the individual glass fibers and morecomplete coordination of the glass fibers with the elastomeric materialconstituting the continuous phase can be achieved when impregnatingcompositions of the type described above are modified for use as a sizecomposition for application to individual glass fiber filaments,preferably as theyare being formed. For this purpose, treatingcompositions of the type described above are further diluted with waterto provide a solids content within the range of 5-30 percent by weightand are formulated to include a glass fiber anchoring agent.Representative of suitable anchoring agents which can be used in thepractice of this invention are the organo silicons, their hydrolysisproducts and polymerization products (polysiloxane) of an organo silanehaving the formula:

wherein Z is a readily hydrolyzable group such as alkoxy having one tofour carbon atoms, e.g., methoxy, ethoxy, propoxy etc., or halogen, suchas chlorine, n is an integer from 1 to 3, and R is hydrogen or anorganic group in which at least one R group is an alkyl group having oneto ten carbon atoms, such as methyl, ethyl, propyl, etc.; alkenyl havingone to ten carbon atoms, such as vinyl, allyl, etc.; cycloalkyl havingfour to eight carbon atoms, such as cyclopentyl, cyclohexyl, etc.; arylhaving six to ten carbon atoms, such as phenyl, naphthyl, benzyl, etc.;alkoxy alkyl, such as methyloxyethyl, etc.; alkenylcarbonyloxyalkyl,such as carbonylpropylmethoxy, etc.; as well as the amino, epoxy,mercapto and halogen derivatives of the foregoing groups.

Illustrative of suitable silanes are ethyltrichlorosilane,propyltrimethoxy silane, vinyl trichlorosilane, ally] triethoxy silane,cyclohexylethyltrimethoxy silane, phenyl trichloro silane, phenyldimethoxy silane, gammamethacryloxypropyl-trimethoxy silane,gammaaminopropyltriethoxy silane, beta-aminovinyldiethoxy silane,N-(gamma-triethoxysilylpropyl)-propylamine, gamma-aminoallyltriethoxysilane, para-aminophenyltriethoxy silane,N-(beta-aminoethyl)-gammaaminopropyl-trimethoxy silane,gamma-chloropropyltrichlorosilane, gamma-glycidoxy propyltrimethoxysilane, 2,4-epoxy-cyclohexylethyltrimethoxy silane, gammamercaptopropyl-trimethoxy silane as well as a wide variety of others. Itwill be understood that the foregoing may be used in the form of thesilane, the silanol or the polysiloxane formed by one or more of theforegoing materials.

Instead of organo silicon as described above, use can also be made ofWerner complex compounds containing a carboxylato group coordinated withthe trivalent nuclear chromic atom, and in which the carboxylato groupmay also contain an amino group or an epoxy group. Suitable Wernercomplex compounds include stearato chromic chloride, methacrylatochromic chloride, gamma-aminopropylato chromic chloride, glycine chromiccomplex or glycylato chromic chloride.

The anchoring agents of the type described above are normally employedin an amount within the range of 0.1 to percent by weight of thetreating composition.

A forming size embodying the concepts of this invention can beformulated as follows:

EXAMPLE 5 2 10 parts by wt. resorcinol-formaldehyde resin 20 60 parts bywt. butadiene-styrene-vinyl pyridine terpolymer l5 40 parts by wt.dicarboxylated butadienestyrene resin 3 30 parts by wt.micro-crystalline paraffin wax 0.1 5 parts by wt. anchoring agentEXAMPLE 6 0.1 3 parts by wt. anchoring agent The solids of the foregoingexamples are formulated in the manner described in Examples 1-4 with theexception that the anchoring agent, such as gammaaminopropyltriethoxysilane, is added to the system after hydrolyzation in aqueous medium, asby use of a quaternary ammonium hydroxide such as tetraethanol ammoniumhydroxide or tetramethyl ammonium hydroxide and that the amount of wateris increased for dilution of the solids to an amount within the range of5-30 percent by weight. When applied as a size, it is possible toachieve a higher loading because of the individual coating of the glassfiber surfaces such that loading in the amount of 1540 percent by weightof the sized glass fibers is possible. i

The following is a specific example of the formulation to provide a sizecomposition.

7 EXAMPLE 7 60 parts by wt. resorcinol-formaldehyde resin by wt. solids)20 parts by wt. formalin 1.5 parts by wt. sodium hydroxide 900 parts bywt. butadiene-styrene-vinyl pyridine terpolymer (42% solids) parts bywt. ammonium hydroxide 350 parts by wt. dicarboxylated butadiene-styreneresin (50% solids) (Pliolite 4121) parts by wt. Vultex Wax Emulsion No.9 (50% solids) 7 parts by wt. gamma-aminopropyltriethoxy silane Sizecompositions of the type illustrated in Examples 5 to 7 can be appliedin any of a variety of conventional methods. The resulting fibers areshown in FIG. 3 of the drawing as formed with a coating 42 of the sizecomposition on the surfaces of the individual glass fibers 40.

When the glass fibers are sized in forming with a composition embodyingthe modification of this invention, the sized glass fibers remainsufficiently non-tacky for processing directly into yarns, strands,cords or fabrics for use in the combination with the continuous phaseelastomer. The sized fibers may be passed directly through a highfrequency, dielectric, hot gas or radiant drying oven as a part of theforming process to insure a non-tacky bundle of coated glass fibers.

In fabricting the combinations of glass fibers, treated in accordancewith the practice of this invention, with elastomeric materials, theglass fibers or bundles of glass fibers are mixed with the elastomericmaterial or otherwise laid down in the desired arrangement forcombination with the elastomeric material, as in the manufacture ofglass fiber-reinforced belts or in the manufacture of rubber tiresreinforced with cords of glass fibers. The combinations of glass fibersand elastomeric materials are then processed in a conventional manner bymolding and curing under heat and pressure or by vulcanizing foradvancement of the elastomeric materials to a cured or vulcanized statewhile in combination with the treated glass fibers whereby the bundlesof glass fibers become strongly integrated with the elastomeric materialin the glass fiber-elastomeric product.

It will be understood that the size compositions, represented byExamples 5, 6, and 7, may also be employed as impregnating compositions,preferably with a lesser dilution by aqueous medium. The anchoring agentwill continue to operate to facilitate the bonded relationship orintegration between the elastomeric material of the glass fiber treatingcomposition and the glass fiber surfaces.

It will be apparent from the foregoing that we have provided a new andimproved composition for use in the treatment of glass fibers andpreferably bundles formed thereof to enhance their utilization withelastomeric materials, even under conditions of high humidity, in themanufacture of glass fiber-elastomeric products while still retainingthe desired degree of nontackiness to enable the treated glass fiberbundle to be processed in substantially the conventional manner intocords, yarns, or fabrics or other arrangements desired for use in thefinal product.

It will be understood that invention exists not only in .thecompositions described but also in the process in which the compositionsare employed in the treatment of glass fibers as well as the treated orimpregnated glass fiber products formed thereof.

It will be understood that changes may be made in the details offormulation and methods of preparation without departing from the spiritof the invention, especially as defined in the following claims.

I claim:

1. A glass fiber bundle comprising a plurality of glass fibers and animpregnant in the bundle, the impregnant comprising 2 to parts by weightof a resorcinolaldehyde resin, 20 to 60 parts by weight of abutadienestyrene-vinyl pyridine terpolymer, to 40 parts by weight of adicarboxylated butadiene-styrene resin having a ratio of styrene tobutadiene of at least 50/50, and 3 to 30 parts by weight of anincompatible wax.

2. A glass fiber bundle as defined in claim 1 wherein the glass fibersforming the bundle have a thin size coating on the surfaces thereof.

3. A glass fiber bundle as defined in claim 1 wherein the impregnantalso includes an anchoring agent.

4. A glass fiber bundle as defined in claim 1 wherein the fiber bundleis in the form of a cord formed of a plurality of strands of glassfibers.

5. A glass fiber bundle as defined in claim 4 wherein the strandsforming the cords are twisted and plied together.

6. A glass fiber bundle as defined in claim 1 wherein the fiber bundleis in the form of a woven or non-woven fabric formed of fibers in theform of cords.

7. A glass fiber bundle comprising a plurality of glass fibers, a thinsize coating on the surfaces of the glass fibers and an impregnant inthe bundle, the impregnant comprising 2 to 10 parts by weight of aresorcinolaldehyde resin, to 60 parts by weight of abutadienestyrene-vinyl pyridine terpolymer, l5 to 40 parts by weight ofa dicarboxylated butadiene-styrene resin having a ratio of styrene tobutadiene of at least 50/50, and

3 to 30 parts by weight of an incompatible wax.

8. Glass fibers having a thin coating thereon, said coating comprising 2to 10 parts by weight of a resorcinol-aldehyde resin, 20 to 60 parts byweight of a butadiene-styrene-vinyi pyridine terpolymer, 15 to 40 partsby weight of a dicarboxylated butadiene-styrene resin having a ratio ofstyrene to butadiene of at least 50/50, and 3 to 30 parts by weight ofan incompatible wax.

9. Glass fibers as defined in claim 8 wherein the coating includes ananchoring agent.

10. In a glass fiber-reinforced elastomeric product in which anelastomeric material constitutes a continuous phase in which the glassfibers are distributed, the improvement in the bonding relationship ofthe glass fibers with the elastomeric material comprising a coating onthe glass fibers formed of 2 to 10 parts by weight of aresorcinol-aldehyde resin, 20 to 60 parts by weight of abutadiene-styrene-vinyl pyridine terpolymer, 15 to 40 parts by weight ofa dicarboxylated butadiene-styrene resin having a ratio of styrene tobutadiene of at least 50/50, and 3 to 30 parts by weight of anincompatible wax.

11. A product as defined in claim 10 which includes an anchoring agentin an amount within the range of 0.1 to 5.0 percent by weight.

12. A product as defined in claim 10 wherein the coating is a coating onthe individual glass fiber filaments.

13. A product as defined in claim 10 wherein the glass fibers are in theform of bundles of glass fibers, and the coating constitutes animpregnant in the bundle.

14. A product as defined in claim 13 wherein the glass fibers formingthe bundles have a thin size coating on the surfaces thereof.

15. A product as defined in claim 13 wherein the bundles are formed ofstrands of glass fibers plied and twisted together.

16. [n a glass fiber-reinforced elastomeric product in which anelastomeric material constitutes a continuous phase in which bundles ofsized glass fibers are distributed, the improvement comprising animpregnant formed of 2 to 10 parts by weight of a resorcinolaldehyderesin, 20 to 60 parts by weight of a butadienestyrene-vinyl pyridineterpolymer, 15 to 40 parts by weight of a dicarboxylatedbutadiene-styrene resin having a ratio of styrene to butadiene of atleast 50/50, and 3 to 30 parts by weight of an incompatible wax.

17. A product as defined in claim 16 wherein the bundles are formed ofstrands of glass fibers plied and twisted together.

2. A glass fiber bundle as defined in claim 1 wherein the glass fibersforming the bUndle have a thin size coating on the surfaces thereof. 3.A glass fiber bundle as defined in claim 1 wherein the impregnant alsoincludes an anchoring agent.
 4. A glass fiber bundle as defined in claim1 wherein the fiber bundle is in the form of a cord formed of aplurality of strands of glass fibers.
 5. A glass fiber bundle as definedin claim 4 wherein the strands forming the cords are twisted and pliedtogether.
 6. A glass fiber bundle as defined in claim 1 wherein thefiber bundle is in the form of a woven or non-woven fabric formed offibers in the form of cords.
 7. A glass fiber bundle comprising aplurality of glass fibers, a thin size coating on the surfaces of theglass fibers and an impregnant in the bundle, the impregnant comprising2 to 10 parts by weight of a resorcinol-aldehyde resin, 20 to 60 partsby weight of a butadiene-styrene-vinyl pyridine terpolymer, 15 to 40parts by weight of a dicarboxylated butadiene-styrene resin having aratio of styrene to butadiene of at least 50/50, and 3 to 30 parts byweight of an incompatible wax.
 8. Glass fibers having a thin coatingthereon, said coating comprising 2 to 10 parts by weight of aresorcinol-aldehyde resin, 20 to 60 parts by weight of abutadiene-styrene-vinyl pyridine terpolymer, 15 to 40 parts by weight ofa dicarboxylated butadiene-styrene resin having a ratio of styrene tobutadiene of at least 50/50, and 3 to 30 parts by weight of anincompatible wax.
 9. Glass fibers as defined in claim 8 wherein thecoating includes an anchoring agent.
 10. In a glass fiber-reinforcedelastomeric product in which an elastomeric material constitutes acontinuous phase in which the glass fibers are distributed, theimprovement in the bonding relationship of the glass fibers with theelastomeric material comprising a coating on the glass fibers formed of2 to 10 parts by weight of a resorcinol-aldehyde resin, 20 to 60 partsby weight of a butadiene-styrene-vinyl pyridine terpolymer, 15 to 40parts by weight of a dicarboxylated butadiene-styrene resin having aratio of styrene to butadiene of at least 50/50, and 3 to 30 parts byweight of an incompatible wax.
 11. A product as defined in claim 10which includes an anchoring agent in an amount within the range of 0.1to 5.0 percent by weight.
 12. A product as defined in claim 10 whereinthe coating is a coating on the individual glass fiber filaments.
 13. Aproduct as defined in claim 10 wherein the glass fibers are in the formof bundles of glass fibers, and the coating constitutes an impregnant inthe bundle.
 14. A product as defined in claim 13 wherein the glassfibers forming the bundles have a thin size coating on the surfacesthereof.
 15. A product as defined in claim 13 wherein the bundles areformed of strands of glass fibers plied and twisted together.
 16. In aglass fiber-reinforced elastomeric product in which an elastomericmaterial constitutes a continuous phase in which bundles of sized glassfibers are distributed, the improvement comprising an impregnant formedof 2 to 10 parts by weight of a resorcinol-aldehyde resin, 20 to 60parts by weight of a butadiene-styrene-vinyl pyridine terpolymer, 15 to40 parts by weight of a dicarboxylated butadiene-styrene resin having aratio of styrene to butadiene of at least 50/50, and 3 to 30 parts byweight of an incompatible wax.
 17. A product as defined in claim 16wherein the bundles are formed of strands of glass fibers plied andtwisted together.